CONVERSION DIRECTE D'EPICHLORHYDRINE EN POLYMERE D'AZIDE GLYCIDYLIQUE

DIRECT CONVERSION OF EPICHLOROHYDRIN TO GLYCIDYL AZIDE POLYMER

Abrégé anglais

ABSTRACT
The invention disclosed is an improved process for the
preparation of hydroxy-terminated aliphatic polyethers having
alkyl azide substituents, such as glycidyl azide polymer. The
improved process involves formation of the polymer in a single
step starting from epichlorohydrin monomer. The reaction is
effected in a suitable polar organic solvent at elevated
temperature for 15 to 24 hours.

Revendications

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED IS DEFINED AS FOLLOWS:
1. A process for the preparation of hydroxy-terminated
aliphatic polyethers having alkyl azide substituents, having a
structural formula
<IMG>
wherein n is an integer from 5 to 10, comprising the single step
of reacting epichlorohydrin with an ionic azide selected from the
group consisting of sodium azide, potassium azide and lithium
azide, in a suitable polar organic solvent at elevated temperature
for about 15 to 24 hours, while agitating.
2. A process as claimed in claim 1, wherein the elevated
temperature is about 70°C - 90°C.
3. A process as claimed in claim 2, wherein the organic
solvent is selected from the group consisting of dimethyl
formamide and dimethyl sulfoxide.
4. A process as claimed in claim 3, wherein the organic
solvent is dimethyl formamide.
5. A process as claimed in claim 4, wherein the ionic azide
is sodium azide.

6. A process as claimed in claim 5, wherein a small amount
of ethylene glycol is included as initiator.
7. A process as claimed in claim 6, including the
additional step of washing the polymer so formed with water.
8. A process as claimed in claim 7, including the further
additional step of purifying the polymer by dissolving the washed
polymer in a suitable organic solvent, drying over magnesium
sulfate and passing through a column containing silica gel.
9. A process as claimed in claim 6, wherein during the
addition of sodium azide heating is effected to about 70°C to
control the initial exothermic reaction, followed by heating to
about 90°C to complete the reaction.
10. A process as claimed in claim 9, wherein the ratio of
dimethyl formamide to epichlorohydrin is about 2:1 and wherein the
reaction time is about 15 hours.
11. A process as claimed in claim 9, wherein the ratio of
dimethyl formamide to epichlorohydrin is about 0.8:1 and wherein
the reaction time is about 24 hours.
12. A process as claimed in claim 5, 10 or 11, wherein the
weight ratio of sodium azide to epichlorohydrin is about 1:1.

Description

~2~
This invention relates -to an improved process for the
synthesis of hydroxy-terminated aliphatic polyethers having alkyl
azide substituents.
Hydroxy-terminated aliphatic polyethers having alkyl
azide substituents are useful as energetic binders and
plasticizers in solid propellants and composite explosives. One
such polyether is glycidyl azide polymer (GAP~. This polymeric
azide is used as an energetic binder (at MW 2000-6000) and as a
plasticizer (at MW o about 500) in composite explosi~es and solid
rocket propellant systems to impart additional energy to -the
formulations, increase the performance and enhance the stability
and the mechanical properties oE the system.
A process or the preparation of hydroxy~terminated
aliphatic polyethers having alkyl azide substituents, e.g. GAP, is
described in United States Patent ~,268,450 of 19 May, 1981, in
the name o-f ~>B. Frankel et al. According to the Frankel et al
process, in a first reaction step, the starting material,
epichlorohydrin (EC~) is polymerized to polyepichlorohydrin (PECH)
using a catalyst, boron trifluoride (BF3) in the presence of a
dichloro compound such as carbon dichloride. In a second step,
PECH is azidized using a molar excess of the order of 2:1' sodium
azide (NaN3) in the presence o a polar organic solvent dimethyl
formamide (DMF) for three days at 100C. It is emphasized that a
molar excess, o about 2:1, of sodium azide is typically employed.
Since sodium a~ide is of a poisonous nature, the use of large
amounts is a distinct disadvantage. A final purification step
using methylene chloride and drying over magnesium sulate is also

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described. This multi step process is costly and -takes Erom -four
to seven days to complete.
According to the invention, a single step process for
the preparation of hydroxy-terminated polyethers having alkyl
azide substituents, e.g. GAP, is provided which is less -time
consuming and more cost effective.
The process according to the invention for the
preparation of hydroxy-terminated aliphatic polyethers having
alkyl azide substituents, having a structural formula
~1 ~ OCH2fH} OH
CH2N3
wherein n is an integer from 5 to 10, comprises the single step of
reacting epichlorohydrin monomer ~CH) with an ionic azide
selected from the group consisting of sodium azide, lithium azide
and potassium azide, in a suitable polar organic solvent at
elevated temperature for about 15 to 24 hours, while agitating.
The preferred ionic azide is sodium azide. Preferab].y,
the weight ratio of sodium azide to ECH is about l:l.
Suitable polar organic solvents include dimethyl
formamide (DME'), and dimethyl sulfoxide (DMSO). A small amount of
ethylene glycol (EG) is used as an initiator.
The reaction temperature is typically in the range of
70 to 90C, with a temperature of about 90C being pre-ferred.
More preferably, an initial exothermic reaction is
allowed to proceed at a temperature of about 70C, followed by
heating to abou-t 90C to complete the reaction. Specifically, the
exothermic reaction arises from the openin~ of the epoxide ring of
'~

ECH which is cause~ by sodium a~ide and proceeds for about thirty
minutes. The "30 minutes" period is approximate and depen~s on
the duratlon of the gradual addition of sodium azide to the
mixture EC~/DMF/EG. It is preferable to heat the reaction mixture
at 70C (approx) during the addition of NaN3 in order to control
the exothermic reaction. Once the sodium azide addition is over
and no sudden rise in temperature is observed, then hea-ting to
90C starts.
Preferably upon cooling, the polymer is washed with
water to remove DMF, EG, unreacted sodium azide and the by-product
sodium chloride. Three waslles with hot water (60C) have been
found appropriate.
Preferably, the washing step is ~ollowed by a
purification step which involves dissolving the polymer in a
suitable organic solvent such as methylene chloride, drying over
magnesium sulfate, and passing through a column containing silica
gel. The solvent is then driven off by heating.
As shown in Table I below, the synthesis of GAP
according to the invention can be accomplished at about 90C in
about 15 hours or in 2~ hours by using less solvent
(DMF/ECH = 0.8). At a reaction temperature lower than 90C, the
quantitative conversion o~ ECH to GAP will re~uire a much longer
reaction time, e.g. 48 hours at 80C and 170 hours at 70C.
. -3-

T~L~ I
T reaction time DMF
(C) (hours) (ECH)
2~0
2~ 0.B
48 2.0
170 2.0
. . .. ~
The hydroxy-terminated a]iphatic polyethers having alkyl
azide substituents prepared according to the invention are of the
lower molecular weight (i.e., average MW of about 500 and
n ~ 5 to 10) variety described aboveO
Example
.
Sodium azide (10g) is gradually added to a mixture of
ECH (10g), DMF (20g) and EG (lg); heating at approximately 70C
and agitation are started. Because of an initial exothermic
reaction, the temperature is controlled during the first 30
minutes (approx) of the synthesis. Once the addition OL sodium
azide is over and no sudden rise in temperature is observed, then
the reaction mixture is heated to 90C and the agitation is
carried out at this temperature for about 15 hours. Heating and
agitation are stopped and the reaction mi~ture is allowed to cool.
The polymer is given three 50 ml hot water (60C) washes to remove
DMF, EG and the salts (sodium azide and sodium chloride). The
polymer is dissolved in 75 ml methylene chloride (MC). The MC
solution is dried over magnesium sulfate and then is passed
through a column containing Sg of silica gel. The resultant
solution is heated to 50C to remove MC and then stripped in
vaccuo to yield 8g (80%) of the GAP polymer: a viscous liquid

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with an amber colour. The GAP was characterized and had the
following properties:
C(35.7); H(5.0); N(39.9); 0(18.7); C1(0.7) wt~
Nitrogen and Chloride analysis o~ the polymer confirmed that
quantitative conversion of ECH to GAP was achieved.
Infrared Spectrum
The IR absorption spectrum of the polymer showed peaks at 4.8 and
8.0 m,u (characteristics of azides).
Weight Average Molecular Weight (Mw) - 540
Number Average Molecular Weight (Mn) - 400
Equivalent Weight (Me) ~ 314
Glass Transition Temperature (Tg) _ -70C
Density - 1.3 g/ml
Hydroxyl Functionality (Mn/Me) - 1.3
Oth0r similar hydroxy-terminated aliphatic polyethers
having alkyl azide substituents may be prepared in a similar
manner by employing other represenative epoxides such as
2,3-epo~ybutane and isobutylene oxide, as the starting material.